m-Toluidine → HCID 68205816, compound

HRID 333530Notes

Reaction equation

HRID 333530 reaction equation
Cl[C:2]1[C:3]([NH:8][CH3:9])=[N:4][CH:5]=[CH:6][N:7]=1.[NH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[C:13]([CH3:17])[CH:12]=1.CC(C)([O-])C.[Na+]>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH3:9][NH:8][C:3]1[C:2]([NH:10][C:11]2[CH:12]=[C:13]([CH3:17])[CH:14]=[CH:15][CH:16]=2)=[N:7][CH:6]=[CH:5][N:4]=1

Participants

7

Reactant 3

HCID 7934m-ToluidineHCID 23676156Sodium t-butoxideHCID 510723073-chloro-N-methyl-2-pyrazinamine(SALTDATA: FREE)

Product 1

HCID 68205816HCID 68205816, compoundYield 30.2%

Reagents, catalysts & solvents 3

HCID 634876Binap, (A+-)-CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Procedure

3-chloro-N-methylpyrazin-2-amine (6 g, 41.8 mmol), m-toluidine (6.72 g, 62.7 mmol), 2,2′-bis(diphenylphosphino)-1,1′-binaphthalene (0.520 g, 0.836 mmol), Pd2(dba)3 (0.383 g, 0.418 mmol), and sodium t-butoxide (6.02 g, 62.7 mmol) were mixed in 200 mL of toluene and degassed for 20 minutes. The mixture was heated to reflux overnight. TLC indicated the reaction did not go to completion. 0.3 g of Pd2(dba)3 and 0.56 g of BINAP was added and heated up to reflux again for 24 h. The reaction was filtered through Celite® and concentrated. The residue was purified by column using 10% ethyl acetate and dichloromethane as solvent to give N2-methyl-N3-(m-tolyl)pyrazine-2,3-diamine (2.7 g, 30.2%).

Workup

  1. customdegassed for 20 minutes
  2. temperatureThe mixture was heated
  3. temperatureto reflux overnight
  4. addition0.3 g of Pd2(dba)3 and 0.56 g of BINAP was added
  5. temperatureheated up
  6. temperatureto reflux again for 24 h
  7. filtrationThe reaction was filtered through Celite®
  8. concentrationconcentrated
  9. customThe residue was purified by column

Sources & evidence

ORD record
ord-e41ef9c5219a4d4c96f694923fb7ab73
Source dataset
uspto-grants-2014_11
Patent number
US08883322B2

Reaction notes

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